Process of producing combined shades on the vegetable fiber and in materials treated according to such process



Patented Aug. 30, 1 927.

UNITED STATES PATENT OFFICE.

GUSTAV PETZOLD AND HEINRICH RITTNER, OF OFFEHBACH-ON-THE-MAIN, GERMANY,

ASSIGNORS TO I. G. FARBENINDUSTRIE AK'IIENGESELLSCHAFT, OF FRANKFURT- ON-THE-MAIN, GERMANY.

PROCESS OF PRODUCING COMBINED SHADES ON THE VEGETABLE FIBER AND I MATERIALS TREATED ACCORDING. TO SUCH PROCESS.

No Drawing Application filed December 15, 1924, Serial No. 756,049, and in Germany January 29, 1924.

ponent and an ester-salt of the leuco com- 5 pound of a Vat dyestufi and the dyestufiis are developed by treatment with oxidizing agents in an acid medium, or the fiber may be impregnated with an alkaline solution of an azo-component and developed with a 20 diazo solution by adding an ester-salt of the leuco-compound of a vat dyestufl' to the paddingor diazosolution and the goods to be dyed may be treated with oxidizing agents in an acid medium. Our invention 25 also relates to the product of such process. Ester-salts of the leuco-compounds ot' vat dyestuffs, which are prepared by transforming leuco compounds of vat dyestuffs into acid esters of a polybasic acid, are described in the U. S. A. Letters Patent No. 1,448,251 of Marcel Bader and Charles Sunder, dated Mar. 13, 1923.

Mixtures of aromatic nitrosamin-alkalisalts and alkalisalts of certain azo compo- 35 nents, some of which are on the market under the-name 0 rapid-fast-colors, are described in the U. S. A. Letters .Patent No. 1,193,566 of Felix Kunert, dated Aug. 8,

1916, and the application Serial No. 717,211

40 of Arthur Zitscher, filed June 2, 1924.

Our invention may be used for dyeing as well as for printing, yielding excellently fast combined colors of different shades, which were not known hitherto, and making it possible to supply the consumer with highly concentrated products immediately ready for use by simple operations. v

In order to illustrate the new process more fully the following examples are g ven.

EXAMPLE 1.

The unprepared goods are printed with the following printing-color:

70 gr. of a paste of the nitrosamin-salt of 5 -nitro-1.2-anisidin, corresponding to 23% of the base are mixed with gr. of caustic soda solution of 36 B.

and

The goods are dried, steamed for a short while and passed into a lukewarm to boiling bath, containing to gr. of sodium bisult'ate, 30 to 40 cc. of a solution of nitrate of iron of 20 Be. in the liter rinsed, soaped and dried.

A brown is obtained.

EXAMPLE 2.

The unprepared-goods are printed with the following printing-color:

92 gr. of a paste, prepared from the 3- inethyl-l-phenyl-5-pyrazolone sodium-salt and the nitrosaminsodiumsalt of 3=nitro-1.4-toluidin, corresponding to 16, 3% of the base, are mixed with 200 gr. ofcold water, poured in 500 gr. of-a neutral tragacanth thickening and then i I 500 gr.

10 gr. of the product, prepared from in- 1 digo according 'to the U. S. A.

Letters Patent No. 1,448,251, dissolved in 198 gr. of water, are added and the whole is made up to.

The goods are dried, steamed for a short while and passed into a dcveloping-bath such as described ample 1, or containing other similar? ing oxidizing agents, rinsed, soape dried.

A yellowish olive is and obtained.

EXAMPLE 3.

The unprepared goods are printed with the whole is made up to i The goods are dried, steamed for a short while and passed into the above mentioned developing-bath, rinsed, soaped and dried. I A greenish olive is obtained. I

EXAMPLE 4. Printing-color for green.

of a paste, containin 15% of diacetoacetyl-ortho-to idin, the nitrosamin-alkalirsalt, of 2.5-dichloroanilin and free caustic soda solution, are stirred with of cold water and poured in of neutral tragacanth thickening,

then

of the product, prepared from indigo according to the .U. S. A. Letters Patent No. 1.448.251, dissolved in I whole is made up to The unprepared oods are printed with this printing-color, ried, steamed in acetic acid for 2 minutes, then passed into the above mentioned developing-bath, rinsed, soaped and r nsed once more,

in connection with Exactortho-nitranilin, v

of a neutral tragacanth thickening of the product, prepared from inof the water, are, added and the In this manner beautiful green shadesof an excellent fastness are obtained.

By using 20 gr. of the product, prepared from dibromindi 0 according to the U. S. A. LettersPatent 0. 1,448,251, for the'printing-color, alittle more yellowish shades of a greater clearness are obtained.

EXAMPLE 5. I Pwinting-color for light-brown.

100 gr of a paste, containing 15% of the anilid of 2.3-hydroxynaphthoic acid, the nitrosamin-alkali-salt of ortho-nitroanilin and free caustic soda solution, are stirred with of cold water and poured in of neutral tragacanth thickening,

then

of the product, prepared fromin- 200v gr. 500 gr.

digo according to the U. S. A.

i solved in 190 gr. of water, are added and the whole is made up to The goods are printed with this printing-' as described in, in acetic acid asse into the developin -bath mentione color in the same manner, Exam le 1, dried, steamed ereinbefore, rinsed, scape more.

In th1s manner.

and rinsed once beautiful light brown Exaurm 6. '3

Dyeing' calico pieces in reddish-brown a aste, containing 15% of the. uni id of 2.3-hydroxynaphthoic acid, the nitrosamin-alkah-salt gr. of

. I of 3-nitro-L4-toluidin and 'free caustic soda solution, are stirred with 200 gr. of cold water and dissolved infurther 500 gr. of water, then 20 gr. of the product,

- digo according to the U.

' Letters Patent No.

solved in prepared from in- S- A gr. of water, are added and the whole is made 'up to iii r. a

The goods are impregnated u n a fou- Letters Patent No. 1,448,251, dis- 1,448,251, die,

shades of an excellent fastness' are obtained.

lard-apparatus with this solution, driedCi 1 hungou' for some hours and then passe intfo the developing-bath mentionedhereine ore.

In this manner a beautiful reddish brown of an excellent iastuess is obtained.

EXAMPLE 7. 10 gr. of 4-nitro-L2-anisidin.are dissolved With g ig gggf i i g i ii :5? prmted with 15 gr. of hydrochloric acid of 22 B. and

f 5 (1 g hth'l n8 hen 100 gr. of boiling Water,

0 g gfg fifi g f p y 160 gr. of ice and after cooling down 30 cc. of caustic soda solution of 34 B., 25 of fi g. mtmte are fi 30 of Turkey red oil and p t e iazotation eing comp e e, 200 gr. of Water, poured in the mass 18 Poured 500 gr. of neutral tragacanth thickening 500 of l 'a tragacanth thlckenlng, and 25, gr. of sodium acetate and I, 10 gr. of the rodu t, pr par d f o i 165 gr. of water are added and the Whole digov according to the U. S. A. 1s made up to Letters Patent No. 1,448,251, dissolved in' 1000 gr. 220 gr. of water, are added and the whole The goods are dried and passed into the is made upto above mentioned developing-bath, rinsed, soaped and dried. 1000 A dark reddish brown is obtalned.

Then the goods are printed with a second printing-color:

10 gr. of 5-cllliloro-2-toluidinare dissolved Wit i of hydrochloric acid of 22 B. and of boiling water, of ice and after cooling down of sodium nitrate 1:4 are added; the diazotation; being complete, the mass is poured in gr. of neutral tragacanth thickening, gr. of sodium acetate and j gr. of Water are added and the Whole is made up to.

gr. gr. cc.

The goods are dried and passed into the above mentioned developing-bath, rinsed, soaped and dried.

A chocolate-brown is obtained.

EXAMPLE 8.

The unprepared goods are printed with: 10 gr. of benzoyl-2. 3-amionaphthol are 'mixed with cc. of caustic soda solution of 34 B., 30 gr. of Turkey red oil and 200 gr. of Water, poured in r 500 gr. of ngutral tragacanth thickening an ll) gr. of the product, prepared from indigo according to the U. S.-A. Letters Patent N 0. 1,448,251, dissolved in i 220 gr. of Water, are added and'the whole is made up to The goods are dried and printed once more with I EXAMPLE 9.

The goods are prepared with a solution of of 12 gr. of 2.5-dichlorophenyl-3-motl1yl-5- pyrazolone in" 15 cc. of caustic soda solution of 34 B. by addition of 10 gr. of Turkey red oil and 8 gr. of the products, prepared from indigo according tov the U. S. A. Letters .PatentNo. 1,448,251, in the liter.

The goods are dried and printed with:

16.5 gr. of 2.5-dichloroanilin are dissolved with of hot Water'and The goods are dried and passed into the above mentioned developing-bath, rinsed, soaped, rinsed and-dried.

A green upon a blue ground is obtained.

EXAMPLE 10.

The goods are prepared with a solution of 10 gr. of aceto-acetyl-anilin in 15 gr. of

caustic soda solution of 34 B. by adding 10 gr. of Turkey red oil in the liter.

' 1b 450 gr.

The goods are dried -10 gr. of

25 gr. 5 5 gr. 350 gr. 30 cc.

70 gr. gr.

and printed with: 5-nitro-1.2-tolu1din are mixed with mass is stirred in of neutral tragacanth thickening, of sodium acetate 1: 1 and of the product, prepared from indigo according to the U. S. A.

Letters Patent No. 1,488,251,- dis solved in of water, are added and the whole is made up to The goods are dried and passed into the above mentioned developing-bath, rinsed, soaped, rinsed and dried. A yellowish green is obtained.

The goods are impregnated of 10 gr. of acetoacetyl-para-anisidin in 15- By'using 10 gr. of the product, prepared from dibromindigo Letters Patent No. above mentioned according to the U. 'S. A. 1,448,251, instead of the EXAMPLE 11.

with a'solution cc. of caustic soda solution 'of 34 B. by

adding 10 The goo gr. of Turkey red oil in the liter. ds are dried and printed with:

10 gr. 7 of the product, prepared from indi:

go according to the U. S. A. Letters Patent No. 1,448,251, dissolved in 490 gr. of water, poured in 500 gr. of neutral tragacanth thickening, I

' made up to I .The goods are dried and printed once more with:

13 gr. of ortho-chloroanilin are dissolved with 30 gr. ofhot water and 30 cc. of hydrochloric acid 20 B.,

140 gr. of cold water,

150 gr. of ice and after cooling down 7. 5 gr.. of sodium nitrite and 30 gr. of water are added; the diazotation being complete the mass is poured in i 450 gr. ofneutral tragacanth thickening, I 50 cc. of sodium acetate 1:1 are added a 1000- gr,

I and the whole is made up to Blue, green and d of 20 B.; the

indigo derivative, a little more yellowish shades of a greater clearness V are obtained.

The cotton The. goods are dried, passed into the above mentioned developing-bath, rinsed, soaped, rinsed and dried. a

yellow printing-efiects on a white ground are obtained.

' EXAMPLE 12.

The cotton oods are prepared with the following pad 'ng-solution and dried: 8 gr.- of. meta-nitroanilid of 2.3-hydroxynaphthoic acid, 10 cc. of caustic soda solution of 34 B., 8 gr. of Turkey red oil, 1 liter.

The goods are then printed with the following printing-color:

10 gr. of meta-nitro-ortho-anisidin (OCH,:NH :NO,-=1:2:4)

are dissolved with 15 gr.

of boiling water and I of ice are, added. Aiter cooling down while stirring of sodium nitrite 1: are added.

the mass is poured m 500 gr. neutralized with 25 gr. of sodium acetate; and I 20 gr; of the product, prepared from indigo according to the U. S. A. Letters' Patent No. "1,448,251, dis-' solved in 145 gr. of water are added and the whole I ismade'upto r' The g are dried, steamed for a short while and assed into the above mentioned develop nth, I

A dark violet of an excellent fastness is obtained. '7 f I Exmrm 13-. r

are pre ared with the following solution and d i d: I I

Padding solufimt 1.

" 10 gr. of diacetoacetyl-ortho-tolidin, 12 cc.

i caustic soda solution of 34 B., 10 gr. of

Turkey red oil, flli'ter.

' The goods are thenpadded with the following solution:

Padding-801M501 2.

50-gr..of the diazo-salt of 2.5-dichloroanilin are dissolved in of water and A of neutral tragacanth thickening, of the product, prepared from indigo according to the Q. S. A. Letters Patent No; 1,448,251, dissolved in of water, are added and thewhole is made up to 300 gr. 400 (gr. 10 gr.

Foo 6 of neutral tragacanth thickening,

of hydrochloric acid of 22 B. and

The diazotation being complete,

rinsed, soaped and dried.

The goods are dried, steamed for a short while and passed into the above mentioned developing-bath, rinsed, soaped, rinsed and dried.

A light green shade of an excellent fastness is obtained.

EXAMPLE 14.

The unprepared goods are printed with the following printing-color'and dried:

Printing-color 1.

of meta-nitroanilid of 2.3 hydroxynaphthoio acid,

of caustic soda solution of 34 B,

of Turkey red oil are dissolved in of boiling water and poured in of neutral tragacanth thickening.

After cooling down of the product, prepared from indigo according to the U. S. A. Letters Patent N 0. 1,448,251, dissolved in of water, are added and the whole is made up to 12 cc. 10 gr. 200 gr. 500 gr.

The goods are printed once more with a second printing-color or padded with a corresponding solution..

Printing-color 2.

50 gr. of the diazo-salt of 2.5 dichloroanilin are dissolved in 450 gr. of water and poured in 500 gr. of a neutral tragacanth thickening and the whole is made up to The goods are dried and passed into a lukewarm to boiling bath, containing 3 gr. of iron chloride, 1 gr. of bichromate, 25 gr. of sodium bisulfate, 1 liter, rinsed, soaped and dried.

A reddish brown of an excellent fastness is obtained.

EXAMPLE 15.

The unprepared goods are printed with the following printing color:

Printing-c0201- 1.

of diacetoacetyl-ortho-tolidin,

of caustic soda solution of 34 B.,

of Turkey red oil are dissolved in of boiling water and poured in of neutral tragacanth thickening.

After cooling down of the product, prepared from indigo according to the U. S. A. Letters Patent No. 1,448,251, dissolved in of water, are added and the whole is made to gr. cc.

gr. gr. gr.

The goods are printed with a second printing-color or padded with a corresponding solution.

Printing-color $2.

10 gr. of meta-nitro-ortho-anisidin (OCH :NH :NO =1:2:4)

' and the components thereof numerous further shades can be obtained.

In the same manner, as the ester-salt of the leuco .derivative of indigo, the corresponding derivatives of the halogenated indigos, thioindigo and other vat dyestufis can be used. As suitable oxidizing agents We may 'mention: hydrogenperoxide, perborates, persulfates or chlorates, chromates and so on.

An appropriate oxidizing agent may also be -added to the printing-colors. Then as developing-baths only accordingly diluted acids orsolutions of salts, acting as acids,

may be used. Certain features of the in vention disclosed herein are claimed in another application filed by us in the United States Patent Ofiice on June 24, 1925, Serial No. 39,377.

Now whatwe claim and desire to secure by Letters Patent is the following:

1. A process of producing combinedshades of azodyestuffs and vat dyestufison the vegetable fiber consisting in producing an azodyestufi' on the fiber, an ester-salt of the leuco-compound of a vat dyestufi' being present simultaneously, and in treating the fibers with oxidizing agents in an acid medium.

2. Materials dyed with a mixture of an azodyestufi' and a vat dyestufi' according to claim 1.

3. A process of producing combined shades of azodyestufi's and vat dyestuffs on the vegetable fiber-consisting in impregnating the fiber with a mixture of an aromatic .nitresamin-alkali-salt and an alkali-salt of an azo-component and an ester-salt of the leucocompound of a vat dyestuff and in deoxidizing agents 1n an acid medium.

'4. Materials dyed with, a mixture of an veloping the dyestufls by treatment with In testimony, that we claim the foregoing as our invention, we have signed our names,

this 29th day of'November, 1924.

GUSTAV vPETZOLD. HEINRICH RITTNER. 

